Electron Injection Dynamics of Ru Polypyridyl Complexes on SnO2


Electron Injection Dynamics of Ru Polypyridyl Complexes on SnO2...

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7088

J. Phys. Chem. B 2005, 109, 7088-7094

Electron Injection Dynamics of Ru Polypyridyl Complexes on SnO2 Nanocrystalline Thin Films Xin Ai, Neil A. Anderson,§ Jianchang Guo, and Tianquan Lian* Department of Chemistry, Emory UniVersity, Atlanta, Georgia 30322 ReceiVed: September 1, 2004; In Final Form: December 10, 2004

Ultrafast infrared spectroscopy was utilized to investigate the electron-transfer dynamics from Ru(dcbpy)2(X)2 complexes (dcbpy ) 4,4′-dicarboxy-2,2′-bipyridine; X2 ) SCN-, 2CN-, and dcbpy; referenced as RuN3, Ru505, and Ru470, respectively) to nanocrystalline SnO2 films. For both films exposed to air (dry) and submerged in a pH 2 buffer solution, all traces show biphasic dynamics with a small ultrafast component (less than 10%) and nonexponential slow component, indicating that most injection occurs from thermalized excited state of the dye. In the dry film, the injection rate becomes slower, comparing RuN3, Ru505, and Ru470, correlating with decreasing excited-state oxidation potentials in these dyes. However, the variation of injection rate with dye potential is less noticeable at pH 2. The possible reason for the different injection dynamics in these dyes and under different environments are discussed. These injection dynamics are also compared with those on TiO2 and ZnO.

Introduction Interfacial electron transfer (ET) dynamics of molecular adsorbate/semiconductor nanoparticle systems has been investigated intensely in recent years. The interest has stemmed from the desire to obtain a fundamental understanding of the process as well as the practical need to improve dye-sensitized solar cell (DSSC) performance.1-4 In a DSSC device, charge separation and recombination dynamics at the adsorbate/semiconductor interface play a crucial role in determining the overall cell efficiency.5,6 Solar cells based on Ru(dcbpy)2(NCS)2 (abbreviated as RuN3, dcbpy ) 4,4′-dicarboxy-2,2′-bipyridine)sensitized TiO2 nanocrystalline porous films have demonstrated a high light-to-electric energy conversion efficiency of about 10%,5,7 and near unity of incident-photon-to-current conversion efficiency (IPCE) value at the peak wavelength.4,8,9 For this reason, ET in the RuN3/TiO2 system has been extensively studied10-23 and is known to occur on the ultrafast time scale, consisting of a fast component (